EP3744800A1 - Solvent-containing emulsified alkyd resin coating composition for glaze and lacquer coatings - Google Patents

Abstract

Solvent-based coating compound for lacquer coatings and glazes, in particular for architectural paints or components thereof, containing or consisting of at least one oxidatively drying organic binder selected from the group consisting of at least one oxidatively drying medium oil and / or long oil alkyd resin, in particular an oxidatively drying long oil alkyd resin, at least a primary dryer based on iron, in particular comprising or consisting of at least one organic salt of iron and / or a complex compound of iron, in particular a complex salt of iron, at least one first secondary dryer, in particular comprising or consisting of at least one organic and / or inorganic salt or a compound of zirconium, magnesium, calcium, strontium, barium, zinc, lithium or aluminum, solvent, water, at least one emulsifier, optionally at least one customary additive.

Description

The present invention relates to a solvent-borne, emulsified, one-component coating composition for glazes and lacquer coatings based on alkyd resins and a coating system containing this solvent-borne emulsified coating composition. The coating composition according to the invention is also based on a coating formed from the coating composition according to the invention and the use of these solvent-containing emulsified coating compositions for the production of glazes and lacquer coatings.

Paint coatings for indoor and outdoor applications, for example on metal or wood substrates, have to meet a wide range of requirements. In addition to an attractive appearance, sufficient resistance to mechanical influences is also desirable. Weather influences should also not lead to impairments. In addition, it is regularly stipulated that the coating compositions which provide these coatings can be applied easily and without problems and, moreover, dry quickly with the formation of a smooth, high-quality surface. For indoor applications in particular, there is increasing demand for coating compounds which are characterized by a low VOC content and, in particular, are also low in odor.

Solvent-containing alkyd resin coatings are known in the prior art. They are used, for example, for white or color painting on structures and surfaces and the like, both indoors and outdoors. They should be easy and even to apply, dry quickly and homogeneously and at the same time develop a smooth, undisturbed surface. In particular, they should show the desired color tone in the long term, i.e. not tend to yellow or discolour.

A solvent for the purposes of the invention is any solvent other than water which is suitable for alkyd resin compositions.

Known solvent-containing coating compositions based on alkyd resins contain at least one organic solvent, but no relevant proportions of water.

Alternatively, coating compounds can be designed as aqueous systems; water-thinnable wood protection paints based on alkyd resins are known, for example. The known aqueous systems usually also contain organic solvents, but in smaller quantities.

Both water-based and solvent-based alkyd resin coating compounds must comply with the Decopaint Directive (European Directive 2004/42 / EC) with regard to their content of volatile organic substances.

The drying of solvent-based coating compounds is usually based on physical and chemical drying or curing processes. For the purpose of initiating and accelerating the chemical, i.e. Oxidative drying using atmospheric oxygen is often used to add organic cobalt salts as so-called primary dryers. In view of the increasingly strict legal requirements, there are some the question of whether such cobalt-based dryers (siccatives) can still be used in future in solvent-based coating compounds for toxicological reasons.

It is also known that when such primary dryers are used, aldehydes are released during the oxidative drying process. These aldehydes or their breakdown products sometimes contribute to odor nuisance and are often problematic from a health point of view.

In addition, the use of organic cobalt salts as siccatives often causes yellowish or greenish color changes when drying, particularly in the case of white or very light colors. As an alternative to cobalt siccatives, the use of manganese-based siccatives is known. Manganese siccatives, however, have the disadvantage that they can lead to changes in color to reddish or pink discoloration.

Iron-based primary dryers, which are harmless to health, do not lead to undesirable color changes. However, iron siccatives have the disadvantage that they do not achieve favorable drying times in connection with the known solvent-based (anhydrous) alkyd resin systems. The Drying times are - especially with long-oil alkyds - far too long and not acceptable for practical use.

Furthermore, silicon dioxide-based matting agents are often used in such coating compositions. Silicon dioxide (SiO2) can also be contained in such coating compounds for other reasons. This is disadvantageous for the following reasons.

It would therefore be desirable to be able to fall back on solvent-based coating compositions which no longer suffer from the disadvantages of the prior art.

The present invention was therefore based on the object of making solvent-based coating compositions for lacquer coatings and glazes, in particular for building lacquers or components thereof, available that provide coatings that dry quickly with little pollutant and / or odor and change in color, above all. White color, do not change and which can preferably be easily applied to a variety of substrates and are also suitable for indoor applications.

It has now been found that the disadvantages of the known coating systems can be overcome if, instead of cobalt- or manganese-based siccatives, siccatives are used which are based on iron or iron compounds. This was countered by the observation that iron-based siccatives lead to long drying times in solvent-based (water-free) alkyd resin coating systems. Iron siccants, however, work reasonably well in water-based alkyd resin paints and produce satisfactory drying times there. An influence of the polarity of the water as a solvent on the effectiveness of the siccative can be assumed here.

However, such aqueous systems have different, mostly poorer properties with regard to application, appearance and protective function, so that they are not always suitable as a substitute for solvent-based alkyd resin coating compounds, which generally have no relevant water content.

However, it has surprisingly been found that the use of iron-based siccatives even in solvent-containing coating compositions based on alkyd resins does not lead to any disadvantages in terms of drying time, namely when the coating composition has a minimum content of water. To solve this The object is to provide the solvent-containing alkyd resin coating compound with a water content which is higher than in the prior art and preferably at least 4.0% by weight, based on the total weight of the coating compound. This solvent-containing alkyd resin coating composition is preferably converted into a "water-in-oil emulsion".

• mindestens einem oxidativ trocknenden organischen Bindemittel, ausgewählt aus der Gruppe bestehend aus mindestens einem oxidativ trocknenden kurz-, mittel- oder langöligen Alkydharz, insbesondere einem oxidativ trocknenden langöligen Alkydharz,
• mindestens einem Primärtrockner basierend auf Eisen, insbesondere umfassend oder bestehend aus mindestens einem organischen Salz des Eisens und/oder einer Komplexverbindung des Eisens, insbesondere einem Komplexsalz des Eisens,
• mindestens einem Sekundärtrockner, insbesondere umfassend oder bestehend aus mindestens einem organischen Salz des Zirkoniums, Strontiums, Calciums, Magnesiums, Bariums, Zinks, Lithiums oder Aluminiums,
• Lösemittel,
• Wasser,
• mindestens einem Emulgator und
• gegebenenfalls mindestens einem üblichen Additiv.

We have found that this object is achieved by a solvent-borne emulsified one-component coating composition containing or consisting of

• at least one oxidatively drying organic binder selected from the group consisting of at least one oxidatively drying short, medium or long oil alkyd resin, in particular an oxidatively drying long oil alkyd resin,
• at least one primary dryer based on iron, in particular comprising or consisting of at least one organic salt of iron and / or a complex compound of iron, in particular a complex salt of iron,
• at least one secondary dryer, in particular comprising or consisting of at least one organic salt of zirconium, strontium, calcium, magnesium, barium, zinc, lithium or aluminum,
• Solvents,
• Water,
• at least one emulsifier and
• optionally at least one customary additive.

The effect of the primary dryer is based on the redox-active passage of a catalytic cycle in which the metal cations assume several oxidation states and radicals are formed from the oxygen in the air via peroxides.

In iron primary dryers, these redox processes usually work well in water-based and aqueous (polar) systems, but poorly or not at all in solvent-based (anhydrous) systems.

Suitable primary dryers based on iron include organic salts of iron as well as metal soaps of iron. Preferred metal soaps here are salts based on cationic iron species and fatty acids, in particular synthetic fatty acids. Examples of suitable fatty acids are hydroxystearates, behenates, arachinates, palmitates and laurates.

Suitable complex compounds of iron, especially complex salts, are based, for example, on 3,7-diaza-bicyclo [3.3.1] nonane ligands. Iron (2 +) - chloro (dimethyl-9,9-dihydroxy-3-methyl-2,4-di- (2-pyridyl) -7- (pyridin-2-ylmethyl) -3.7-diazabicyclo may be exemplified as particularly suitable [3.3.1] called nonane-1,5-dicarboxylate) chloride. Its manufacture is in WO 2011095308 A1 disclosed.

Iron-based primary dryers are commercially available, for example from the manufacturer Borchers GmbH.

The iron primary dryer content is generally 0.0001 - 0.3% by weight, better 0.0001 - 0.1% by weight, even better 0.0001 - 0.05% by weight (in terms of metal content) .

It has been shown that in solvent-containing one-component coating compositions based on alkyd resin when using a siccative comprising at least one organic salt of iron and / or a complex compound of iron with at least one oxidatively drying organic binder selected from the group consisting of at least one oxidatively drying medium oil and / or long oil alkyd resin, in particular an oxidatively drying long oil alkyd resin, with good drying performance, very low-odor and discoloration-free coatings can be obtained.

Particularly good drying performance combined with pronounced color stability of the coatings are generally associated with the use of at least one iron primary dryer together with at least one first secondary dryer, preferably comprising at least one organic and / or inorganic salt or a compound of zirconium, magnesium, calcium, strontium, Bariums, zinc, lithium or aluminum.

The content of secondary dryer is generally (with regard to metal content) at 0.01-3.0% by weight, better 0.05-2.0% by weight, even better 0.1-1.6% by weight., based on the total weight of the coating compound. When using a first and a second secondary dryer, their contents are each half of these values.

Particularly suitable coating compositions according to the invention comprise at least one second secondary dryer comprising or consisting of at least one organic salt of calcium, zinc, zirconium and any mixture thereof. Particularly satisfactory results are regularly obtained when an organic salt of calcium is used as a so-called "through dryer" in addition to an organic salt of zirconium, a so-called "auxiliary dryer".

In a particularly suitable embodiment, it can be provided that the organic salt of the secondary dryer comprises neodecanoates, oleates, stearates, palmitates, octoates and / or naphthenates, in particular neodecanoates, particularly preferably zirconium neodecanoates.

The compositions according to the invention are preferably essentially free from cobalt and manganese compounds, in particular from siccatives based on cobalt and manganese. “Essentially” here preferably means cobalt and manganese contents (in relation to the metal content) of below 0.01% by weight, more particularly of less than 0.001% by weight, based on the total weight of the composition. Particularly preferably, the compositions do not contain any cobalt or manganese compound contents that can be detected using customary analytical methods such as EDX, WDX and / or AAS.

For the oxidatively drying organic binder, preference is given to using those binders which are selected from the group of at least one oxidatively drying medium oil and / or long oil alkyd resin, in particular an oxidatively drying long oil alkyd resin, at least one oxidatively drying modified, in particular isocyanate-modified or amine-modified medium oil and / or long oil alkyd resin, in particular an oxidatively drying modified long oil alkyd resin, and any mixture thereof.

The alkyd resin content of the composition, possibly including thixotropic alkyd resin, is generally 10-80% by weight, better 12-60% by weight, even better 14-50% by weight, based on the total weight of the composition.

In a particularly expedient embodiment, use is made of the oxidatively drying long oil alkyd resins. In the context of the present invention, a long-oil alkyd resin is to be understood as meaning those long-oil systems which have a Have an oil content or an oil length above 60%. In contrast, a short-oil alkyd resin is to be understood as meaning a short-oil compound that is regularly in the range of 20-40% over an oil content or oil length. In this context, the oil content or the oil length, in relation to the total weight of the alkyd resin, is to be understood as the percentage by weight of those fatty acids, including the polyol residue, which are present in the alkyd resin in connection with the hydroxyl groups of the polyol unit. For the purposes of the present invention, the terms "oil content" and "oil length" are used synonymously.

In addition to the at least one oxidatively drying organic binder selected from the group consisting of at least one oxidatively drying medium-oil and / or long-oil alkyd resin, particularly suitable coating compositions according to the invention also contain at least one oxidatively drying modified medium-oil and / or long-oil alkyd resin. Preferred oxidatively drying, modified, medium-oil and long-oil alkyd resins can be selected from the group consisting of siliconized alkyd resins, acrylated alkyd resins, isocyanate-modified alkyd resins and any mixtures thereof.

Furthermore, in connection with the long oil content of the oxidatively drying long oil alkyd resins, it can be provided that these are based on linoleic acid, linolenic acid and / or oleic acid, optionally with the addition of palmitic acid. Among the oxidatively drying long oil alkyd resins, those are particularly preferred in order to achieve the object on which the invention is based, which, determined in accordance with DIN 53241-1, have an iodine number not greater than 120, in particular not greater than 100, preferably in the range from 20 to 120 or 20 to 100, preferably in the range from 40-80, in each case based on 100% solids of the binder.

The long / medium oil alkyd resins are often used in the coating compositions of the invention in solution in hydrocarbons, in particular in dearomatized or isoparaffinic hydrocarbons.
The solvent used for the solvent-based coating composition according to the invention is preferably at least one, in particular essentially aromatic-free, aliphatic hydrocarbon, preferably from the group consisting of, in particular dearomatized white spirit, n-paraffins, isoparaffins, cycloparaffins and any mixtures thereof. If necessary, methoxypropoxypropanol can also be added as a co-solvent. Dearomatized aliphatic hydrocarbons are particularly preferably used. The solvent is usually present in the coating composition according to the invention in an amount in the range from 10 to 40% by weight, preferably in the range from 15 to 45% by weight. Methoxypropoxypropanol is often added as a co-solvent, in particular to improve the dilution properties and to obtain a good processing viscosity, for example in an amount in the range from 0.5 to 8% by weight, preferably in the range from 1 to 5% by weight.

Solvents or hydrocarbons that belong to TRGS 900 group 1 according to the definition TRGS900 are to be understood as aromatic-free in the context of the present invention. According to the VDL guideline for building paints (guideline for the declaration of ingredients in building varnishes, building paints and related products) VDL-RL01 (6th revision) of the Association of the German Paint and Printing Ink Industry, in particular such solvents or aliphatic hydrocarbons should also be aromatic-free within the meaning of the present Invention are understood that lead to coatings from the coating compositions according to the invention which have an aromatic content of less than 1% by weight, determined according to DIN 55683. In the context of the present invention, aromatic-free solvents or aliphatic hydrocarbons should very preferably be understood as having an aromatic content of less than 0.2% by weight, preferably less than 0.1% by weight.

The composition contains at least one emulsifier, preferably a polymeric emulsifier and particularly preferably an emulsifier based on a film-forming polysaccharide resin. Such emulsifiers are preferred because they are "bio-based", that is, they are based on naturally occurring substances or are similar to such substances. In addition, such emulsifiers are solids that cannot be emitted as VOCs themselves or make a contribution to VOC emissions. They are firmly built into the matrix and thus practically "polymerized". The use of such polymeric, preferably film-forming emulsifiers makes it possible to advantageously lower the VOC content of the coating, since the alkyd resin system can now be diluted with water and part of the solvent can thus be replaced by water.
At the same time, the use of these emulsifiers reduces the tendency of the alkyd product to yellow.

Suitable such emulsifiers are, for. B. available under the name Lorama LPR.

These emulsifiers are preferably in the form of a colloidal dispersion (solid-in-liquid). The solids content in the dispersion is generally between 15 and 60% by weight, preferably between 18 and 50% by weight and particularly preferably between 30 and 48% by weight.

The emulsifier is preferably used in an amount of 0.1-10 wt.%, Better 0.2-8 wt.%, Even better 0.25-5 wt.%, Based on the total amount of the composition.

The composition contains water to form a 'water-in-oil emulsion', the water content is generally 2-40% by weight, better at 3-35% by weight, even better at 4-30% by weight, best at 4 - 10% by weight.

Advantageous coating compositions according to the invention are also distinguished by the fact that they also contain at least one anti-skinning agent. The anti-skinning agents usually act as reducing or complexing agents and prevent premature curing of the coating composition on the surface in the containers. Preferred anti-skinning agents can be selected from the group consisting of substituted phenols, dialkylaminoethanol, in particular dimethylaminoethanol and / or diethylaminoethanol, dialkylhydroxylamine, in particular dimethylhydroxylamine and / or diethylhydroxylamine, dibenzylhydroxylamine, hydroxymanone, diethylamine, triethylamine, ketoxanone, any, butanone oxime, in particular, diethylamine, triethylamine, diethylamine, triethylamine, diethylamine, triethylamine, diethylamine, triethylamine, or any other Mixtures thereof.

The content of anti-skinning agents, matting agents, light stabilizers, radical scavengers, etc. in the composition is generally 0.1 - 8.0% by weight, better 0.2 - 6.0% by weight, even better 0.3 - 5, 0% by weight, based on the total weight of the composition.

For some applications it has proven to be expedient to equip the coating composition according to the invention with at least one rheology modifier. Preferably, no thickeners are used selected from the group consisting of modified and unmodified sheet silicates, such as bentonites. Among the rheology modifiers, preference is given to using thixotropic alkyd resins.

For the purposes of the present invention, thixotropic alkyd resins include, for example, those alkyd resins which result from a partial reaction of polyamides from polymeric fatty acids and polyamines with alkyl resins, so-called polyamide-modified ones Alkyd resins. Furthermore, polyurea-modified alkyd resins, also called polyurea thixotropic alkyd resins, can be used as thixotropic alkyd resins for the purposes of the invention. As an example, reference is made to suitable thixotropic alkyd resins, as described in EP 922738B1 are described. With the aid of these rheology modifiers, in particular with the aid of thixotropic alkyd resins, the stability of the coating films obtained with the coating compositions according to the invention can be further improved.

The content of thixotropic alkyd resin is generally 0.1-20 wt.%, Better 0.5-15 wt.%, Even better 1.0-12 wt.%, Based on the total weight of the composition, preferably as part of the total content Alkyd resin.

For a number of applications, the coating compounds according to the invention can also have at least one filler, in particular selected from the group consisting of carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, sulfates, in particular barium sulfate, and oxides such as aluminum oxide and mixtures thereof.

But now it has been shown that above all At low water contents, the presence of SiO2 and SiO2-based compounds also proves to be a problem with regard to drying times. The iron siccatives are no longer as effective as expected and the drying times are significantly longer. On the surface of SiO2 particles, for example of amorphous silicas, the reversibility of the oxidation and reduction processes of iron in its various oxidation states seems to be hindered or even blocked. It is known that oxidation level 3 of iron can be stabilized on SiO2 surfaces. A reduction to Fe (II) is difficult. Only when a larger amount of water is added to the solvent-based alkyd resin coating composition does the SiO2 surfaces appear to be at least partially "deactivated" so that the undesirable interactions between the iron siccative and the SiO2 surface are reduced.

Because of this interaction of the iron siccatives with SiO2 surfaces, the coating compositions according to the invention are therefore preferably essentially free of silicon dioxide-based, amorphous fillers such as silica, silica gel, amorphous SiO2, microsilica and / or glasses, which are also used as matting agents. It is also advantageous if no SiO2-based, crystalline fillers such as quartz or cristobalite are contained, if these fillers are in very fine form are present, ie with an average particle size value D50 of less than 10 μm (determined according to ISO 13320). The same applies to other silicate fillers, in particular silicates, as well as feldspar, pyrophyllite and serpentine and their mixtures if their silicon dioxide content is greater than 60% by weight based on the molar mass of the silicate filler.

“Silicon dioxide-based” in the context of this invention means an SiO2 weight fraction of greater than 90% by weight based on the total molar mass of the substance in question. "Essentially free" in this context means less than 1.0% by weight based on the total weight of the coating compound, better less than 0.5% by weight based on the total weight of the coating compound, even better less than 0.1% by weight based on the Total weight of the coating compound, preferably below the analytical detection limit, for example using XRD and / or EDX.

For a number of embodiments of the coating compositions according to the invention, matt coatings can be obtained with these. In many cases, however, it has proven advantageous to obtain a matt appearance of the coating surface by also adding at least one matting agent to the coating composition according to the invention. In general, the matting agents used are often silica, in particular precipitated silica, pyrogenic silica, amorphous silica and particularly preferably aftertreated precipitated silica. For the reasons already outlined, these silicas should not be contained in the coating composition according to the invention. The coating compound according to the invention should be free of these SiO2 compounds within the scope of the analytical detection limit. Waxes are preferably suitable as matting agents, in particular polyolefin waxes such as polyethylene or polypropylene waxes, preferably with a particle size D90, determined in accordance with ISO 13320, in the range 5-15 μm. Such waxes are used with contents of 0.2-7.5% by weight, better 0.3-5.5% by weight, even better 0.4-4.5% by weight, based on the total weight of the composition .

For the purpose of suitable color adjustment, the coating compositions according to the invention are generally mixed with at least one colorant as an alternative or in addition. Pigments (white or colored pigments) are preferred among the colorants. Titanium dioxide is preferred among the white pigments.

The content of pigments / dyes is generally 0.1-50% by weight, better 0.2-45% by weight, even better 0.5-40% by weight, based on the total weight of the composition.

Compositions according to the invention preferably have a pigment volume concentration (PVC) according to EN ISO 4618-1 of 0 to 50%, more preferably 2 to 45%, particularly preferably 4 to 40%.

In an expedient embodiment of the coating compositions according to the invention, the additives are selected from the group consisting of defoamers, deaerators, thickeners, light stabilizers, radical scavengers, wetting / dispersing agents, slip / leveling additives, surface additives, in particular silicone surface additives, for example polyether-modified polymethylalkylsiloxane and / or silicone polyether copolymers and / or surface-active polyacrylates, waxes and / or surface-active polyacrylates and any mixtures of these compounds.

So-called HALS compounds (hindered amine light stabilizers) can be used as suitable light stabilizers. These compounds often enable very good weather stability and often they are accompanied by a reduced tendency to chalk. Light stabilizers can e.g. can be used in an amount in the range from 0.1 to 2.0% by weight, preferably in the range from 0.2 to 1.0% by weight, based in each case on the total face of the coating composition.

Wetting agents and dispersants can be added to the coating compositions of the invention in order to stabilize the pigments and / or fillers and, for example, to prevent pigments and fillers from settling out. Wetting and dispersing agents regularly help to ensure that the pigments and / or fillers do not reagglomerate. The addition of wetting agents and dispersants can improve storage stability. The dispersibility can also be improved by stabilizing the pigments or preventing agglomeration with the aid of wetting and dispersing agents. Furthermore, the wetting and / or dispersing agents can, for example, help to improve hiding power. Suitable wetting agents include, for example, the salts of unsaturated polyamides and / or the salts of acidic polyesters, in particular of low molecular weight acidic polyesters.

Polysiloxanes, for example, can be used as defoamers. Suitable foam-destroying or foam-suppressing polysiloxanes are known to the person skilled in the art.

The coating compositions according to the invention are particularly suitable for use as architectural paints or as a constituent thereof. The coating compound according to the invention can be a primer, topcoat coating compound or a transparent or semitransparent final coating compound or a component thereof. These coating compounds are used indoors and / or outdoors.

The coating composition according to the invention can be used as so-called 1-pot coating compositions. It can be used as a primer as well as a middle layer and as a top coat. It is also of particular advantage that the coating compositions according to the invention manage completely without siccatives based on cobalt and / or lead, but nevertheless show an excellent drying profile. With the coating compositions according to the invention, very storage-stable systems are obtained which do not tend to gel even after a prolonged storage period.

The coating according to the invention has an average, in particular absolute, dry layer thickness, determined according to DIN EN ISO 2808-2 (May 2017), not above 100 μm, preferably not above 80 μm and particularly preferably in the range from 5 to 60 μm.

The solvent-based emulsified coating composition according to the invention can be prepared in a 1-pot reaction common to the person skilled in the art. For this purpose, the components are mixed in a suitable sequence in a reaction vessel.

In a preferred embodiment, however, part of the alkyd resin binder is converted into a separate aqueous emulsion, so that a water-in-oil emulsion is created as a semi-finished product or preliminary product. This emulsion is then combined with a conventional solvent-containing (water-free) alkyd resin formulation to form the coating composition according to the invention. The water-in-oil emulsion as a semi-finished product contains the alkyd resin, solvent, emulsifier and water as well as possibly additives such as defoamers and deaerators, etc. The semi-finished product is stable in storage and can be produced in advance.

• Alkydharz
  • 10 - 80 Gew.%, besser 12 - 60 Gew.% , noch besser 14 - 50 Gew.% Alkydharz thixotrop
  • 0,1 - 20 Gew.%, besser 0,5 - 15 Gew.% , noch besser 1,0 - 12 Gew.% Füllstoffe
  • 0 - 40 Gew.%, besser 0 - 35 Gew.% , noch besser 0 - 30 Gew.% Pigmente / Farbstoffe
  • 0,1 - 50 Gew.%, besser 0,2 - 45 Gew.% , noch besser 0,5 - 40 Gew.% Additive: Netz- / Dispergiermittel, Entlüfter, Entschäumer, Gleit- / Verlaufsadditive, Hautverhinderungsmittel, Mattierungsmittel, Lichtschutzmittel, Radikalfänger, etc.
  • 0,1 - 8,0 Gew.%, besser 0,2 - 6,0 Gew.% , noch besser 0,3 - 5,0 Gew.% Lösemittel
  • 1,0 - 40 Gew.%, besser 2,0 - 35 Gew.% , noch besser 3,0 - 30 Gew.% Eisen-Primärtrockner (in Bezug auf Metallanteil)
  • 0,0001 - 0,3 Gew.%, besser 0,0001 - 0,1 Gew.% , noch besser 0,0001 - 0,05 Gew.%
• Sekundärtrockner (in Bezug auf Metallanteil)
  • 0,01 - 3,0 Gew.%, besser 0,05 - 2,0 Gew.% , noch besser 0,1 - 1,6 Gew.% Wasser
  • 2 - 90 Gew.%, besser 3 - 70 Gew.%, noch besser 4 - 50 Gew.%, am besten 4 - 10 Gew.%
• Emulgator
  0,1 - 10 Gew.%, besser 0,2 - 8 Gew.%, noch besser 0,25 - 5 Gew.%.

Composition of coating material in general:

• Alkyd resin
  • 10 - 80% by weight, better 12 - 60% by weight, even better 14 - 50% by weight alkyd resin thixotropic
  • 0.1-20% by weight, better 0.5-15% by weight, even better 1.0-12% by weight fillers
  • 0-40% by weight, better 0-35% by weight, even better 0-30% by weight pigments / dyes
  • 0.1 - 50 wt.%, Better 0.2 - 45 wt.%, Even better 0.5 - 40 wt.% Additives: wetting / dispersing agents, deaerators, defoamers, slip / leveling additives, anti-skinning agents, matting agents, light stabilizers , Radical scavengers, etc.
  • 0.1 - 8.0 wt.%, Better 0.2 - 6.0 wt.%, Even better 0.3 - 5.0 wt.% Solvent
  • 1.0 - 40 wt.%, Better 2.0 - 35 wt.%, Even better 3.0 - 30 wt.% Iron primary dryer (in relation to metal content)
  • 0.0001 - 0.3 wt.%, Better 0.0001 - 0.1 wt.%, Even better 0.0001 - 0.05 wt.%
• Secondary dryer (in terms of metal content)
  • 0.01-3.0% by weight, better 0.05-2.0% by weight, even better 0.1-1.6% by weight water
  • 2 - 90 wt.%, Better 3 - 70 wt.%, Even better 4 - 50 wt.%, Best 4 - 10 wt.%
• Emulsifier
  0.1-10 wt.%, Better 0.2-8 wt.%, Even better 0.25-5 wt.%.

Embodiment 1: White lacquer, semi-gloss: according to the invention

Alkyd resin 20 wt.% Alkyd resin thixotropic 2 wt.% water 8 wt.% Emulsifier 1 wt.% Fillers 16 wt.% Pigments / dyes 32 wt.% Additives: wetting / dispersing agents, deaerators, defamers, slip / leveling additives, anti-skinning agents, light protection agents, radical scavengers, etc. 4.8 wt.% Matting agent (PE wax) 3.0 wt.% Solvent 12.8% by weight Iron primary dryer (in terms of metal content) 0.0003 wt% Zirconium siccative (auxiliary dryer) 0.2 wt.% Calcium siccative (through dryer) 0.2 wt.%

White lacquer, semi-gloss: Reference example 1

Alkyd resin 24 wt.% Alkyd resin thixotropic 2 wt.% Fillers 16 wt.% Pigments / dyes 32 wt.% Additives: wetting / dispersing agents, deaerators, defoamers, slip / leveling additives, anti-skinning agents, light protection agents, radical scavengers, etc. 4.8 wt.% Matting agent (amorphous silica) 3.0 wt.% Solvent 17.8% by weight Iron primary dryer (in terms of metal content) 0.0003 wt% Zirconium siccative (auxiliary dryer) 0.2 wt.% Calcium siccative (through dryer) 0.2 wt.%

Reference example 1 contains no water and therefore also no emulsifier. The matting agent polyethylene wax was exchanged for amorphous silica.

As reference example 2, the matting agent polyethylene wax was exchanged for amorphous silica in the formulation according to the invention for the semi-gloss white varnish, and a conventional cobalt primary dryer was used in the usual amount instead of the iron primary dryer.

The coating compositions (according to the invention, reference example 1 and reference example 2) were applied with a 75 μm doctor blade and examined with a drying recorder. The coating composition according to the invention had dried sufficiently after about 3.5 hours; reference example 2 after about 8 hours. In the case of reference example 1, on the other hand, no drying was found after 24 hours, and the test was terminated.

Embodiment 2: Surface glaze white: according to the invention

Alkyd resin 28 wt.% Alkyd resin thixotropic 12 wt.% water 14 wt% Emulsifier 2 wt.% Pigments / dyes 8 wt.% Additives: wetting / dispersing agents, deaerators, defoamers, slip / leveling additives, anti-skinning agents, light protection agents, radical scavengers, etc. 3.6 wt.% Matting agents 2.0 wt.% Solvent 30 wt.% Iron primary dryer (in terms of metal content) 0.0004 wt% Zirconium siccative (auxiliary dryer) 0.25 wt.% Calcium siccative (through dryer) 0.15 wt%

The coatings obtained from the coating compositions according to the invention show no discoloration tendencies. It is also of practical relevance that film hardnesses can be set with the coating compositions according to the invention, as they are usually set when using conventional cobalt-based primary dryers.

Another advantage of the coating compositions according to the invention is the lowering of the VOC content. Less solvent has to be used because some of it is substituted by water. For example, the coating compositions according to the invention for decorative applications even lead to VOC values below 300 g / L. The standard DIN EN ISO 11890-1 (September 2007) can be used to determine the content of volatile organic compounds (VOC content).

Claims (17)

Solvent-based coating material for lacquer coatings and glazes, in particular for building lacquers or components thereof, containing or consisting of
at least one oxidatively drying organic binder selected from the group consisting of at least one oxidatively drying medium oil and / or long oil alkyd resin, in particular an oxidatively drying long oil alkyd resin,
at least one primary dryer based on iron, in particular comprising or consisting of at least one organic salt of iron and / or a complex compound of iron, in particular a complex salt of iron,
at least one first secondary dryer, in particular comprising or consisting of at least one organic and / or inorganic salt or a compound of zirconium, magnesium, calcium, strontium, barium, zinc, lithium or aluminum,
Solvents,
Water,
at least one emulsifier,
optionally at least one customary additive. The coating composition of claim 1 further comprising
at least one second secondary dryer comprising or consisting of at least one organic salt of calcium, zirconium and any mixture thereof, the first and the second secondary dryer being different. Coating compound according to Claim 1 or 2, which is essentially free from cobalt and manganese compounds, in particular from siccatives based on cobalt and manganese. Coating compound according to one of the preceding claims, characterized in that the oxidatively drying organic binder also has at least one oxidatively drying modified medium-oil and / or long-oil alkyd resin, in particular selected from the group consisting of siliconized alkyd resins, acrylated alkyd resins, isocyanate-modified alkyd resins and any mixtures thereof , in particular isocyanate-modified long oil alkyd resins. Coating compound according to one of the preceding claims, characterized in that the solvent, in particular aromatic-free, aliphatic hydrocarbons, preferably selected from the group consisting of, in particular dearomatized white spirit, n-paraffins, isoparaffins, cycloparaffins and any mixtures thereof, comprises or consists and preferably Contains methoxypropoxypropanol as a co-solvent. Coating compound according to one of the preceding claims, characterized in that the additive is selected from the group consisting of defoamers, light stabilizers, radical scavengers, wetting agents, dispersants, surface additives, in particular silicone surface additives, for example polyether-modified polymethylakylsiloxane and / or silicone polyether copolymers and / or surface-active polyacrylates, Matting agents, especially waxes, and any mixtures of these compounds. Coating compound according to one of the preceding claims, characterized in that the organic salt of the first and / or second secondary dryer comprises neodecanoates, oleates, stearates, palmitates, octoates and / or naphtenates, in particular neodeconoates, particularly preferably zirconium and / or strontium neodecanoates. Coating compound according to one of the preceding claims, characterized in that the long oil content of the oxidatively drying long oil alkyd resins is based on linoleic acid, linolenic acid, oleic acid and palmitic acid and / or that the middle oil content of the oxidatively drying middle oil alkyd resins is based on linoleic acid, linolenic acid and / or oleic acid and, if necessary, below Addition of palmitic acid, especially linoleic acid, linolenic acid, oleic acid and palmitic acid, is based. Coating compound according to one of the preceding claims, characterized in that the coating compound is essentially free of amorphous silicon dioxide and SiO ₂ -based compounds. Coating compound according to one of the preceding claims, characterized in that the proportion of the primary dryer based on iron, in relation to its metal proportion, is in the range from 0.0001 to 0.3 percent by weight, preferably in the range from 0.0001 to 0.1 percent by weight and particularly preferably in the range from 0.0001 to 0.05 percent by weight, based in each case on the total weight of the coating compound, the proportion of the at least one first secondary dryer comprising or consisting of at least one organic salt of zirconium, strontium, calcium, magnesium, barium , Zinc, lithium and / or aluminum, in relation to its metal content, is in the range from 0.005 to 1.5 percent by weight, preferably in the range from 0.025 to 1.0 percent by weight and particularly preferably in the range from 0.05 to 0.8 percent by weight , in each case based on the total weight of oxidatively drying organic binders, and / or that
the proportion of the at least one second secondary dryer comprising or consisting of at least one organic salt of calcium, lithium, zirconium and any mixture, in relation to its metal proportion, of which in the range from 0.005 to 1.5 percent by weight, preferably in the range from 0, 01 to 3.0 percent by weight and particularly preferably in the range from 0.025 to 0.8 percent by weight, based in each case on the total weight of oxidatively drying organic binders, and / or that
the proportion of solvent is in the range from 0.1 to 40 percent by weight, preferably 0.2 to 35 percent by weight and particularly preferably in the range from 3 to 30 percent by weight, based on the total weight of the coating composition. Coating compound according to one of claims 1 to 10, with a content of at least one emulsifier, preferably a polymeric emulsifier and particularly preferably an emulsifier based on a film-forming polysaccharide resin, especially in an amount of 0.1-10% by weight, better 0.2 - 8% by weight, even better 0.25-5% by weight. Coating compound according to one of Claims 1 to 11, with a water content of 2 - 40% by weight, better 3 - 35% by weight, even better 4 - 30% by weight, most preferably 4 - 10% by weight. Coating compound according to one of the preceding claims, with a pigment volume concentration (PVC) according to EN ISO 4618-1 of 0 to 50%, more preferably 2 to 45%, particularly preferably 4 to 40%. Coating on a substrate, in particular topcoat coating, primer coating, primer / topcoat 1-pot coating or transparent or semitransparent final coating, obtained or obtainable by applying and physically and chemically drying the coating composition according to any one of claims 1 to 13. Coating according to claim 14, characterized in that this over an average, in particular absolute, dry layer thickness, determined according to DIN EN ISO 2808-2 (May 2017), not above 100 µm, preferably not above 80 µm and particularly preferably in the range of 5 to 60 µm. Use of a coating compound according to one of Claims 1 to 13 for the production of glazes and lacquer coatings. Process for the production of a coating composition according to one of claims 1 to 13, in which a water-in-oil emulsion is first produced from alkyd resin, solvent, water and emulsifier and optionally additives such as defoamers and deaerators and this is then used to produce the coating composition a corresponding proportion of a conventional solvent-based and anhydrous alkyd resin formulation is combined.